Metallized ortho-hydroxy, ortho amino monoazo dyestuffs



Patented Jan. 29, 1952 METALLIZED'" ORTHO-HYDROXY, ORTHO AMINO MONOAZO DYESTUFFS Heinrich H. Bestehorn, Easton, Pa., and Jack F. Morgan, Phillipsburg, N. .L, assignors to General Aniline & Film Corporation, New York, N. Y., a. corporation of Delaware No Drawing. Application December s, 1947,

Serial No. 789,556

This invention relates to new metallized ortho-hydroxy, ortho-amino monoazo dyestulfs, which dyestuffs are capable of dyeing nylon (linear-polyamide) in deep shades.

Apart from the qualities of the "dyeing, it is known that nylon may be dyed with most dyestuffs which dye wool. Among such, the metallized, water-soluble, acid, monoazo dyestuffs have beenrecommended for the purpose. However, as it is also known, these dyestuffs have certain,

drawbacks for the dyeing of nylon, the dyeing being not as deep as might be desired and of limited fastness to light and washing.

We have now found a group of new metallized ortho-hydroxy,ortho-amiho monoazo compounds which are outstanding in their properties as dyestuffs for nylon. The newcompounds are free from sulfonic acid groups and are further characterized by containing a single carboxy group, which group is located in the diazo component of the dyestufi and in non-ortho position to the azo bridge, i. e.- in non-chelating position. The new compounds have the general formula:

wherein a: is a carboxy group innon-orthov positionto the am bridge, 1/ is hydrogenlor an alkyl, alkoxy, halogen or nitro radical; sis hydrogen oran alkyl, alkoxy or halogen radical; R is hydrogen or an alkyl radical, and Me'is a'metal in complex combination with the azo bridge, which metal may be chromium, copper, cobalt or nickel.

The new dyestuffs are capable of dyeing nylon in deep shades of excellent fastness to light and washing, the carboxy group promoting affinity of the dyestuffs for nylon. They are not as soluble in water as the known metallized acid monoazo dyestuffs carrying a sulfonic acid group, yet

3 Claims. (01. zed-r149) monoa'zo dyestuffs which, in the one instance, contain a chelated carboxy group and, in the other, a plurality of carboxy groups but none in chelation. They are further distinguished from the aforementioned dyestuffs containing a chelated carboxy group in possessing better stability in acid bath and better exhaust. They are, moreover, similar enough intheir dyeing properties to the dyestuffs now used in the trade to allow dyeings' to be made on nylon with-a mixture of the old with the new dyestuifs.

The new compounds may be prepared in the way known for the manufacture of metallized ortho-hydroxy, or'tho-amino 11101103210 dyestufis, the coupling being done in alkaline medium. The diazo component is derived from an unsulfonated hydroxy-amino benzoic acid wherein the hydroxy and amino groups are in ortho position to each other and the single carboxy group is in non-ortho position to the amino group, the nuc'leusof the hydroxy-amino benzoic acids being otherwise unsubstituted, or substituted by an alkyl, alkoxy, halogen or nitro group, for example, 3-amino salicylic acid, 3-hydroxy-4-aminobenzoic acid, 4-hydroxy-3-aminobenzoic acid, 5- chloro-3-amino salicyclic acid, 4-amino-3-hyairoxy-Z-methyl benzoic acid, 5-nitro-3-amino salicylic acid, 5-amino-4-hydroxy 3 methoxy ff" R...

wherein a and R have the significance aforesaid. The resulting ortho-hydroxy,ortho-amino monoazo dyestufl is then metallized. V

Coupling compounds for the new dyestuffs are in part known in the literature and can be prepared using the general methods described in German Patents 49,060, 44,792, 44,002, 76,419, 48,151 and 82,765.

Suitable N-alkylamino and N-dialkylaminophenols, unsubstituted in the nucleus, are for example, m methylaminophenol, m dimethylaminophenol, 'm-ethylaminophenol, m-diethylaminophenol, and the like.

V Meta-aminophenols substituted in the nucleus by" an alkyl, alkoxy or halogen group, which can be employed as coupling compounds for the new dyestu'fis are, for example, 3-methylamino-ocresol, 5-diethylamino-o-cresol, 3methylaminoguaicol, S-dimethylaminoguaicol, ,2-chloro-3- ethylaminophenol, 5-dimethylamino-3-hydroxyanisole, 5-methylamino-3-hydroxyphenetole, 5- dimethylamino-m-cresol, S-d'imethylamino e ,3- hydroxy o-xylene, 5-chloro3-diethylaminophe- 1101 and the like. Obviously, other known methods can be employed for preparing alkyl,

tion'of the dyestuff, it may be accomplished in Depend- 1 alkaline, neutral or acid medium. While we prefer to'carry out the metallization in an aqueous medium, it can also be effected in an organic solvent, as for example, alcohol, :orsin mixtures of :such solvents with :one another or with watenl The dyeing of nylon with the new compounds canbe carried out in a neutral or preferably a slightly acid bath. .The dyeing can be-carried out at temperatures in the .dyebath of about 190 F. 'to the-boiling point. .For acidification of the dyebath there can be used; acetic, formic" and the like acids.

Advantageously, substances. which in aqueous solution dissociate on heating to liberate free acid, e.g., ammonium thiocyanate,

diethyl .tartrate and the like, can also be em- ;ployed for the acidification of the dyebath. A

specific illustration of the mode of dyeing nylon" with the :new dyestufis isas follows. ,A solution .of one of the new dyestuils is preparedby heating to the boil ng Point 0.15 part of the dyestufi with .300 parts -of water containing a suitable surface active agent, e. .g.,, approximately 0.1% of the .oleic acid amide of .methyl taurine, sodium .salt. --Five parts of nylon are entered into the hot dye- :bath and heating continued. After 15 minutes, 5 parts of 1% acetic acid solution is added and a like amount 'af-ter another-l5.minutes the bath vbeingslightly acid after these additions. After about 1 hour total heating time the nylon is removed mm the d'yebath, rinsed .in warm, water and soaped by immersing it in a hot solution .of :5 parts of .a 10% green soap .solutioninBOO parts of water, The dyed nylon :is again rinsed and then dried and conditioned in the usual manner.

The invention is further illustrated by the 01- lowing specific examples to which, however, it is not intended that it be limited.

Example 1 19 grams of 3-aminosal'icyclic acid, hydrochloride are diazotized in the usual manner, e. g., by dissolving it in300 m1. of water and 15 ml. of cone. hydrochloric acid, cooling and adding 6.9 grams .of sodium nitrite as solution. .The

, diazo suspension is then poured into a solution .0117 grams of m-diethylaminophenol dissolved in .800 ;ml. of water, 5 grams :of sodium hydroxide cobaltous chloride (6H2O) dissolved in 200 ml.

of water. After stirring .for gihours at 50-60 .C.., the cobalt dye is filtered off. Itis converted to its sodium salt by treatment with an aqueous solution of the equivalent quantity .of sod'iu m formula is obtained hydroxide, dried, and ground to a fine powder. It has the probable formula:

and dyes nylon from acid bath an orange-red shade.

Example 2 1 When in the above example, 22.6 grams of 5- chloro-B-aminosalicyclic acid hydrochloride is used in place of the 3-aminosalicyclic acid hydrochloride as ..starting material for the diazo component, a cobalt dyestufi of the probable l I I which dyes nylon from acid bath an .attractiye ibluish redshade.

By replacing tlie cobad-tous chloride :in the above examples by copper sulfate or :nickelons sulfate respectively, the corresponding copper and nickel dyestufis are obtained, zdyeing nylon in various shades. The chromium metal com-- plex may be obtained by res'ludging 'ithe v dye paste in 1700 water with chromium formate and heating in a pressureimsselat C. for 4 hours.

we ciaimz i l. A metallized :ortho-hydroxy, .ortho-amino monoazo dyes-tun of the :general formula;

lower alkyl 7 3,1 7 3 Me wherein a: is a single carboxy group in non-ortho position to the azo bridge, 3 is a memberselected from the group consisting of hydrogen and the lower alkyl, lower .alkoxy, halogen and' ni tro radicals, e is a member selected .f-rom the group consisting .of hydrogen and the lower alkyl, lower alkoxy and halogen radicals, 'R is a member" selected from the group consisting of hydrogen and a lower alkyl radical, and Me is a metal complex combination Withthe azo bridge selected from the group consisting of chromium, coppcif. c'obalt'andnickel; I 2. The metallized ortho-hydroxy, ortho amino *monoazo dyestu-ii of the "forum-la: 'I i I ($2 5):

recon o-fi-on .3. The .metallized ortho-hyd roxy, .orthoeamino monoazodyestufiof thetormula: y

(grHal-z Hemmer: H. .iBESTiEHQE-N.

' snot; MORGAN.

- ,(neterences on following page) L 5 REFERENCES CITED FOREIGN PATENTS The following references are of record in the Number Country Date file of this patent: 77,077 Switzerland Mar. 16, 1918 UNITED STATES PATENTS 5 OTHER REFERENCES Number Name Date Textile Colorist, December 1943, pages 551 and 2,117,731 Kollmann et a1. May 17, 1938 552,

2,277,551 Kirst Mar. 24, 1942 re Prutton, 1914 C. D. 727, 533, O. G. 755. 

1. A METALLIZED ORTHO-HYDROXY, ORTHO-AMINO MONOAZO DYESTUFF OF THE GENERAL FORMUAL: 